Asymmetric substitution changes the UV-induced nonradiative decay pathway and the spectra behaviors of β-diketones.
作者： Yonggang Yang , Donglin Li , Chaozheng Li , Yufang Liu , Kai Jiang
DOI: 10.1016/J.SAA.2018.09.026
关键词: Surface hopping 、 Excited state 、 Spectral line 、 Molecular physics 、 Photoisomerization 、 Conformational isomerism 、 Proton 、 Chemistry 、 Molecule 、 Conical intersection
摘要: Asymmetric substitution has not been termed as an essential factor in studying photo-induced ultrafast dynamics of molecular system. 4-hydroxybut-3-en-2-one (HEO), together with symmetric malonaldehyde (MA) and acetylacetone (AA), have provided target sample to study the nonradiative decay (ND) processes β-diketones. An effective ND pathway three molecules is presented that their excited second (S2) states transfer first (S1) state by nonadiabatic surface hopping, then triplet (T1) crossing minimum energy point (MECP), after which ground (S0) through MECP. More importantly, asymmetric HEO induces proton S1 generates a proton-transferred conformer lowest energy, does occur for MA AA. This change exploits new decays transferred T1 undergoes reverse S0 MECPs between states. The two pathways give detailed geometric information on hopping S2/S1 S1/T1/S0, interpret reason while spectra emission. result significantly different from previous reported photoisomerization or conical intersection work shows changes structure behaviors.
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